JP2709762B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a method for forming a super-high contrast negative image using a stable developer having a low pH, which contains a hydrophobic hydrazine compound stably. And a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art The presence of a hydrazine compound in a silver halide emulsion layer for various purposes is described in, for example,
Theory of the Photographic Proess, "Third Edition, (19
66) 281 pages, Research Disclosure Magazine 23
510 (1983); U.S. Pat.
No. 243739, No. 4272614, No. 432364
3, No. 4,385,108 and No. 4,268,969. That is, the hydrazine compound is sometimes used to form a positive image directly in combination with an internal latent image type silver halide, or separately from a surface latent image type silver halide in combination with a high sensitivity. Can be used to form a super-high contrast negative image.

However, in the method using the hydrazine compound, the pH of the developing solution is set very high,
There is a problem that the H value tends to fluctuate, and the fluctuation of the pH value tends to cause variation in the result of photographic characteristics. U.S. Pat. Nos. 4,988,604 and 4,994,365
In order to solve the above-mentioned problem, it is described that the activity of the hydrazine compound is increased so that the effect of sensitizing and increasing the contrast of the hydrazine compound can be exhibited with a developer having a lower pH.

When a hydrazine compound is used in a silver halide light-sensitive material, the hydrazine compound should not be eluted into a developing solution to cause contamination of the solution or adversely affect silver halide in a nearby emulsion layer. It is desirable to use a hydrazine compound which is resistant to diffusion, that is, water-insoluble. However, it is not easy to stably disperse the water-insoluble hydrophobic hydrazine compound in a hydrophilic silver halide emulsion.

Heretofore, as a method for dispersing a hydrophobic photographic additive in a silver halide emulsion, there has been known a method in which the additive is dissolved in a water-miscible organic solvent such as methanol and added to the emulsion. However, due to low solubility in water,
Precipitation occurs at the time of addition, or dispersibility during coating deteriorates,
Further, there is a problem that the film quality is deteriorated or the reactivity of the hydrazine compound is reduced. U.S. Patent No. 4,
988,604 and 4,994,365 also do not solve this problem because a large amount of a hydrophobic hydrazine compound is added to a silver halide emulsion.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material containing a hydrophobic hydrazine compound stably dispersed so as to sufficiently fulfill its purpose of use.

[0007]

An object of the present invention is to provide a hydrazine compound represented by the following general formula (1) and an anionic surfactant represented by the following general formula (6) or (7). This has been attained by a silver halide photographic light-sensitive material characterized by including:

[0008]

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In the formula, L ₁ and L ₂ represent a —CONR ₇ — group,
NR ₇ CONR ₈ — group, —SO ₂ NR ₇ — group or —N
Represents an R ₇ SO ₂ NR ₈ — group, which may be the same or different (here, R ₇ and R ₈ are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms) Represents a group). m is 0 or 1. L ₃ is -C
H ₂ CH ₂ O—, —CH ₂ CH (CH ₃ ) O—, or —CH ₂ CH (OH) CH ₂ O—, where n is 3
Is an integer greater than or equal to. R ₃ , R ₄ , and R ₅ are a divalent aliphatic group or an aromatic group or a divalent aliphatic group or an aromatic group, or an —O— group, a —CO— group,
It is a divalent group formed by combining an —S— group, a —SO— group, a —SO ₂ — group, and a —NR ₉ — group (R ₉ has the same meaning as R ₇ ). R ₆ represents an aliphatic group or an aromatic group. G ₁ is a —CO— group, a —COCO— group, a —CS—
_{Groups, -C (= NG 2 R 2} ) - group, -SO- group, -SO ₂
— Or —P (O) (G ₂ R ₂ ) —. G ₂ is a mere bond, —O— group, —S— group, or —N (R ₂ )
Represents a group, R ₂ represents an aliphatic group, an aromatic group or a hydrogen atom, and when a plurality of R ₂ are present in a molecule, they may be the same or different. One of A ₁ and A ₂ is a hydrogen atom, and the other is a hydrogen atom or an acyl group, an alkyl or an arylsulfonyl group.

[0010]

[0011]

[0012]

[0013]

As R ₇ and R ₈ , a hydrogen atom is preferable. R ₃ is preferably an alkylene group having 1 to 10 carbon atoms or a combination thereof with a —S— group, a —SO— group, a —SO
_A divalent group formed by combining _2- groups,
R ₄ and R ₅ are preferably an arylene group having 6 to 20 carbon atoms. Particularly, R ₅ is preferably a phenylene group. R
₃ , R ₄ and R ₅ may be substituted, and preferred substituents include, for example, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, a ureido group, a urethane group, Aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carboxylic acid An amide group,
A sulfonamide group, a carboxyl group, a phosphoric acid amide group and the like are mentioned. Preferred substituents are a linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms) and an aralkyl group (preferably having 7 carbon atoms). To 30), an alkoxy group (preferably having 1 to 30 carbon atoms), a substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 30 carbon atoms), an acylamino group (preferably having 2 carbon atoms). , A sulfonamide group (preferably having 1 to 40 carbon atoms), a ureido group (preferably having 1 to 40 carbon atoms), a phosphoric amide group (preferably having 1 to 40 carbon atoms) ).

[0015]

In the general formula (1), G ₁ represents a —CO— group,
-SO ₂ - group are preferred, -CO- group is most preferred. A ₁ , A
₂ is preferably a hydrogen atom.

In the formula (1), the alkyl group represented by R ₂ is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group (for example, a benzene ring). Including). G ₁
If is -CO- group, preferred among the groups represented by R ₂ is a hydrogen atom, an alkyl group (e.g., methyl group,
Trifluoromethyl group, 3-hydroxypropyl group, 3
A methanesulfonamidopropyl group, a phenylsulfonylmethyl group, an aralkyl group (eg, an o-hydroxybenzyl group), an aryl group (eg, a phenyl group, a 3,5-dichlorophenyl group, an o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group,
And a hydrogen atom is particularly preferable. R ₂ may be substituted;
As the substituent, the substituents listed for R ₃ , R ₄ and R ₅ can be applied. R ₂ may also be such as to cause a cyclization reaction that cleaves the G ₁ -R ₂ moiety from the residual molecule to form a cyclic structure containing atoms of the -G ₁ -R ₂ moiety. For example, Japanese Patent Application Laid-Open No. 63-29
No. 751 and the like.

R ₆ or R _{2 in} the general formula (1) may have a ballast group or polymer commonly used in immobile photographic additives such as couplers incorporated therein. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties. For example, the ballast group is selected from an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. Can be. Further, as a polymer, for example, JP-A-1-1005
No. 30.

R ₆ or R _{2 in} the general formula (1) may have a group in which a group which enhances adsorption to the surface of silver halide grains is incorporated. Examples of such an adsorptive group include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, and triazole groups such as U.S. Pat.
No. 4,459,347, JP-A-59-195,233.
Nos. 59-200, 231 and 59-201, 04
No. 5, 59-201, 046, 59-201, 0
No. 47, 59-201, 048, 59-201,
Nos. 049, 61-170, 733, 61-27
Nos. 0,744, 62-948, 63-234,2
No. 44, No. 63-234, No. 245, No. 63-234,
No. 246.

The compounds of the general formula (1) of the present invention are described, for example, in JP-A-61-213,847 and JP-A-62-260,153.
No. 4,684,604, Japanese Patent Application No. 63-9 / 1988.
No. 8,803, U.S. Pat. Nos. 3,379,529, 3,620,746, 4,377,634, 4,332,878, and JP-A-49-129,536.
Nos. 56-153,336 and 56-153,34
No. 2, U.S. Pat. Nos. 4,988,604 and 4,994,
It can be synthesized by using the method described in, for example, US Pat. The compounds used in the present invention are listed below, but the present invention is not limited thereto.

[0021]

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[0022]

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[0023]

[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

The compound of the formula (1) of the present invention may be added in an amount of 1 × 10 ^-6 to 5 × 1 per mol of silver halide.
It is preferably contained in an amount of 0 ^-2 mol, and particularly preferably in the range of 1 x 10 ^-5 mol to 2 x 10 ^-2 mol.

The compound of the general formula (1) according to the present invention can be used in a suitable water-miscible organic solvent such as an alcohol (methanol, methanol, etc.).
It can be used by dissolving in ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, methylcellosolve and the like. Also, dibutyl phthalate,
Oils such as tricresyl phosphate, glyceryl triacetate or diethyl phthalate, dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone,
An emulsified dispersion can also be prepared and used mechanically. Alternatively, a redox compound powder can be dispersed in water using a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method.

The anionic surfactant suitable for use in the present invention is a surfactant containing an acidic group such as a carboxyl group, a sulfo group, a phospho group, a sulfate group, and a phosphate group. HLB value of 8 to 14 (here, the HLB value is based on the organic / inorganic method. For details, see Tsuji, "Techniques of emulsification and solubilization", 3rd edition (197
9) See pages 10 to 11 issued by Kogyo Tosho Co., Ltd.). The representative examples of the anionic surfactant preferably used in the present invention are shown below, but the present invention is not limited to these.

[0035]

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Here, R ¹⁰ is a saturated or unsaturated hydrocarbon having 3 to 20 carbon atoms and its fluorine-substituted product, and R ¹¹ is a hydrogen atom, a methyl group, an ethyl group or a propyl group. n is an integer of 1 to 20, particularly preferably 1 to 8. M is 1
It is a valent alkali metal, and Na and K are particularly preferable.

[0037]

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R ¹⁰ , M and n have the same meanings as in the general formula (6). a represents 0.1 or 2. m is an integer of 1 to 6, particularly preferably 2 to 4.

[0039]

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R ¹⁰ and M have the same meanings as in formula (6).

[0041]

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However, R ¹¹ and M have the same meanings as in the general formula (6), and m has the same meaning as in the general formula (7).

[0043]

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R ¹⁴ is a saturated or unsaturated hydrocarbon in which a hydrogen moiety having 3 to 22 carbon atoms is fluorinated, and preferably has 7 to 18 carbon atoms. R ¹¹ and M have the same meanings as in the general formula (6), and m has the same meaning as in the general formula (7).
Specific examples of anionic surfactants that are particularly preferably used are as follows.

[0045]

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[0046]

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[0047]

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[0048]

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The photosensitive silver halide emulsion used in the present invention may have any composition such as silver chloride, silver chlorobromide, silver iodobromide and silver iodochlorobromide. The photosensitive silver halide used in the present invention preferably has average grain size fine grains (for example, 0.7 μm or less), and particularly preferably 0.5 μm or less. The particle size distribution is basically not limited, but is preferably monodispersed. The term “monodisperse” as used herein means that at least 95% by weight or the number of particles is composed of a group of particles having a size within ± 40% of the average particle size. The photosensitive silver halide grains in the photographic emulsion may have regular crystals such as cubic or octahedral, or may have irregular crystals such as spherical or plate-like. Or a compound having a complex form of these crystal forms. In the silver halide grains, the inside and the surface layer may be composed of a uniform phase, or may be composed of different phases. Two or more kinds of silver halide emulsions formed separately may be used as a mixture.

The silver halide emulsion used in the present invention contains a cadmium salt, a sulfite, a lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof during the formation of silver halide grains or physical ripening. They may coexist. The emulsion layer or other hydrophilic colloid layer of the present invention may contain a water-soluble dye as a filter dye or for various purposes such as prevention of irradiation. As the filter dye, a dye for further lowering the photographic sensitivity, preferably an ultraviolet absorber having a spectral absorption maximum in the intrinsic sensitivity range of silver halide, or safety against safelight light when handled as a light room photosensitive material 350 nm to 600 nm
A dye having substantial light absorption in the nm region is used. These dyes may be added to the emulsion layer depending on the purpose, or may be added together with the mordant to the non-light-sensitive hydrophilic colloid layer above the silver halide emulsion layer, that is, a layer farther from the silver halide emulsion layer with respect to the support. It is preferable to use it fixed. It depends on the molar extinction coefficient of the dye, but usually 10 ^-2 g
/ M ^{2 to 1} g / m ² . Preferably 50 mg
５００500 mg / m ² . Specific examples of the dye are described in JP-A-63-6
No. 4039, some of which are listed below.

[0051]

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[0052]

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The above dye is dissolved in an appropriate solvent (eg, water, alcohol (eg, methanol, ethanol, propanol, etc.), acetone, methyl cellosolve, etc., or a mixed solvent thereof) to form the non-photosensitive hydrophilic compound of the present invention. It is added to the coating solution for the colloid layer. These dyes are 2
It can be used in combination of more than one species. The dye of the present invention is
It is used in an amount necessary to enable light room handling. The amount of the specific dye is generally ^{10 -3 g / m 2 ~1 g} / m 2, it is possible to find a preferable amount ranges particularly ^{10 -3 g / m 2 ~0.5g /} m 2.

The light-sensitive silver halide emulsion used in the method of the present invention may not be chemically sensitized, but may be. As methods of chemical sensitization of silver halide emulsions, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these can be used alone or in combination with chemical sensitization. Is also good. Among the noble metal sensitization methods, the gold sensitization method is a typical one and uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts such as platinum, palladium and iridium may be contained. Specific examples thereof are described in U.S. Pat. No. 2,448,060 and British Patent 618,061. As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like can be used in addition to the sulfur compounds contained in gelatin. Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer.

A known spectral sensitizing dye may be added to the silver halide emulsion layer used in the present invention. The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging during the manufacturing process, storage or photographic processing of the light-sensitive material or stabilizing photographic performance. Among these, preferred are benzotriazoles (eg, 5-methyl-benzotriazole) and nitroindazoles (eg, 5-nitroindazole). Further, these compounds may be contained in the treatment liquid. The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine) ), Mucohalogenic acids, and the like can be used alone or in combination.

In the photographic emulsion layer or other hydrophilic colloid layer of the photographic material prepared by using the present invention, a coating aid, an antistatic agent, an improvement in slipperiness, an emulsification / dispersion, an adhesion prevention and an improvement in photographic characteristics (for example, development acceleration) For various purposes such as contrast enhancement, sensitization, and the like, various surfactants may be contained. Particularly, the surfactant preferably used in the present invention is described in JP-B-58-99-1.
No. 412, polyalkylene oxides having a molecular weight of 600 or more. Further, a polymer latex such as polyalkyl acrylate can be contained for dimensional stability.

Examples of the development accelerator suitable for use in the present invention or the accelerator for nucleation and infectious development are described in JP-A-53-77.
No. 616, No. 54-37772, No. 53-137, 1
No. 33, No. 60-140, No. 340, No. 60-1495
In addition to the compounds disclosed in No. 9 and the like, various compounds containing an N or S atom are effective. Next, specific examples are listed.

[0058]

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[0059]

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[0060]

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These accelerators depend on the type of the compound.
The optimum amount of addition is different, but 1.0 × 10 ^-3~ 0.5g / m^Two,
Preferably 5.0 × 10^-3~ 0.1g / m^TwoUsed in the range
Is desirable. Using the silver halide photosensitive material of the present invention
To obtain ultra-high contrast photographic properties, use conventional infectious developer or rice.
PH 13 described in National Patent No. 2,419,975
There is no need to use a near high alkali developer, and stable development
Liquids can be used. That is, the halogen of the present invention
Silver halide photosensitive material contains 0.2% of sulfite ion as a preservative.
0 mol / l or more, preferably 0.50 mol / l
PH 10.0-12.3, especially pH 10.5
~ 11.5 developer to produce a very high contrast negative image
Obtainable. Development that can be used in the method of the present invention
There are no particular restrictions on the active substance, such as dihydroxybenze
(For example, hydroquinone), 3-pyrazolidones
(For example, 1-phenyl-3-pyrazolidone, 4,4-di
Methyl-1-phenyl-3-pyrazolidone), aminop
Enols (eg, N-methyl-p-aminophenol)
Can be used alone or in combination.
You. The silver halide light-sensitive material of the present invention is particularly suitable for use as a main developing agent.
Dihydroxybenzenes as auxiliary developing agents
Current containing 3-pyrazolidones or aminophenols
Suitable to be processed with image liquid. Preferably this development
The dihydroxybenzenes in the liquid are 0.05 to 0.5
Mol / l, 3-pyrazolidones or aminophen
Knols are used together in the range of 0.06 mol / l or less.
It is. As an additive used in addition to the above components,
Acids, compounds such as borax, sodium bromide, potassium bromide
And development inhibitors such as potassium iodide: ethylene glycol
, Diethylene glycol, triethylene glycol,
Dimethylformamide, methyl cellosolve, hexylene
Organic solvents such as glycol, ethanol, methanol:
1-phenyl-5-mercaptotetrazole, 5-nitto
Indazole-based compounds such as Lonidazole, 5-methyl
Benztriazole compounds such as benztriazole
Which antifoggant or black pepper inhibitor:
It may contain, if necessary, a color tone agent, a surfactant,
It may contain an antifoaming agent, a water softener, a hardening agent and the like. Departure
The developing solution to be used is described in JP-A-56-106244.
And the amine compounds described in Japanese Patent Application No. 1-291818.
May be included. In the developer of the present invention, a silver stain inhibitor is used.
Use of the compounds described in JP-A-56-24347
Can be. Japanese Unexamined Patent Publication (Kokai) No.
61-267759 can be used.
Wear. Further, as a pH buffering agent used for a developer,
No. 0-93,433 or JP-A No.
No. 186259 can be used.
You. Use a fixing agent with a commonly used composition
Can be Thiosulfates, thiocyanes as fixing agents
Organic salts known to be effective as fixing agents in addition to phosphates
Sulfur compounds can be used. The fixer contains a hardener
Water soluble aluminum (for example, aluminum sulfate,
Vans, etc.). Where water-soluble aluminum
The amount of the salt is usually 0.4 to 2.0 g-Al / liter.
It is. Furthermore, ethylene is used as a trivalent iron compound as an oxidant.
It can be used as a complex with diamine tetraacetic acid. Book
The processing temperature in the process of the invention is usually between 18 ° C and 50 ° C.
Chosen between. It is preferable to use an automatic processor for photographic processing.
Preferably, according to the method of the present invention, the photosensitive material is automatically processed by an automatic developing machine.
90 to total processing time
Even when set to seconds to 120 seconds, the negative gradation of
Photographic properties are obtained.

[0062]

【Example】

Example 1 An emulsion was prepared as follows. An aqueous silver nitrate solution and 4 × 10 4 mol / mol silver in a gelatin aqueous solution maintained at 50 ° C.
Aqueous solution of potassium iodide and potassium bromide containing ^-7 moles of K ₃ IrCl ₆ was added simultaneously over 60 minutes, during which pAg
Was maintained at 7.5 to prepare a monodispersed silver iodobromide emulsion (average grain size 0.28 μm, silver iodide content 0.4 mol%). This emulsion was washed with water according to a conventional method to remove soluble salts, and then potassium iodide was added to the emulsion to convert the grain surface, whereby the average silver iodide content of the grain / the silver iodide content of the grain surface = 1 / Thus, silver iodobromide emulsion No. 3 was obtained.
To this was added phenoxyethanol as a preservative.

This emulsion was used as a sensitizing dye in an amount of 3.times.10.sup.- ⁴ mol of 5,5'-dichloro-9-ethyl-per mol of silver.
3,3'-bis (3-sulfopropyl) oxacarbocyanine sodium salt was added, and 4-
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 5-methylbenzotriazole, and the following compounds (a) and (b) were each added so that 5 mg / m ² could be applied.

[0064]

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Next, as shown in Table 1, an anionic surfactant was added so as to have a concentration of 0.1 mmol / m ² . Thereafter, as shown in Table 1, the hydrazine compound was added as a methanol solution. The hydrazine compound for comparison is as follows.

[0066]

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Further, polyethylene glycol having an average molecular weight of 600 was added to a concentration of 75 mg / m ^2, and a dispersion of polyethyl acrylate was added at a solid content to gelatin ratio of 30 wt.
%, And 1,3-divinylsulfonyl-2-propanol was added as a hard film, and the mixture was coated on a polyethylene terephthalate film so as to have a silver content of 3.5 g / m ² . (2g gelatin
/ M ² ) On top of this, 1.2 g / m ² of gelatin as a protective layer, 40 mg of an irregular SiO ₂ matting agent having a particle size of about 3 μm /
m ² , methanol silica 0.1 g / m ² , polyacrylamide 100 mg / m ² , hydroquinone 200 mg / m ² and silicone oil, the following compounds as preservatives

[0068]

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And phenoxyethanol and a fluorine-containing surfactant represented by the following structural formula as a coating aid.

[0070]

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And a layer containing sodium dodecylbenzenesulfonate were simultaneously applied to prepare samples as shown in Table 1.

The back layer was applied according to the following formulation. [Back layer formulation] Gelatin 4 g / m ² matting agent Polymethyl methacrylate (particle size: 3.0 to 4.0 μ) 10 mg / m ² latex Polyethyl acrylate 2 g / m ² Surfactant Sodium p-dodecylbenzenesulfonate 40mg / m ²

Fluorosurfactant

[0074]

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Gelatin hardener

[0076]

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Dye Mixture of dyes [a], [b] and [c] Dye [a] 50 mg / m ² Dye [b] 100 mg / m ² Dye [c] 50 mg / m ²

[0078]

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The back layer coating solution contains the following compound as a preservative.

[0080]

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And phenoxyethanol.

When the above sample was applied, coating was performed under the following two conditions. Condition 1 A coating solution for a light-sensitive emulsion layer, after adding an additive, apply immediately (within at most one hour). Condition 2 In the coating solution for the photosensitive emulsion layer, additives other than the hardening agent and polyethyl acrylate are added, and the mixture is aged at 40 ° C. for 24 hours. Then, the hardening agent and polyethyl acrylate are added, and coating is performed immediately. Here, in order to evaluate the state of precipitation of the hydrazine compound in the coating solution, the filtration time of the coating solution was measured under the conditions (Note 1) under each of Conditions 1 and 2. After exposing these samples through an optical wedge with tungsten light, an automatic developing machine FG manufactured by Fuji Photo Film Co., Ltd.
The film was developed at -660F for 30 seconds at 34 ° C. using a developing solution having the following composition, and fixing, washing and drying were sequentially performed.

[0083]

[Table 1]

[0084]

[Table 2]

Note 1 Filtration time of coating solution: 100 ml of coating solution
Is the time required for filtration using a microfilter having an average pore diameter of 10 μm and a diameter of 1.2 cm under a pressure of 1 pound / cm ² . Note 2 S in the photographic properties indicates the relative value (relative sensitivity) of the reciprocal of the exposure amount giving a density of 3.0. Note 3 The filter was clogged and only a part of 100 ml could be filtered.

From the results shown in Table 1, in Samples 1-2 and 1-3, as the coating solution ages, precipitates are formed in the solution, causing clogging of the filter and making filtration impossible.
It can be seen that Samples 1-5 and 1-6 of the present invention hardly cause clogging. Further, Samples 1-8 and 1 of the present invention
At -9, it can be seen that the hydrazine compound of the present invention specifically improves the filterability remarkably. Regarding the photographic properties, the hydrazine compound of the present invention (samples 1-5, 1-6) gives sensitivity equal to or higher than that of the hydrazine compound of the comparative example (sample 1-4). Samples 1-5 and 1-6 according to the present invention correspond to Samples 1-2 and 1-3 containing no anionic surfactant.
It can be seen that the sensitivity is increased when no aging (condition 1) is performed, and the change in performance is small even when aging is performed (condition 2). Further, the effect is specifically enhanced by the hydrazine compound of the present invention in Samples 1-8 and 1-9. As described above, in the sample of the present invention, the hydrophobic hydrazine compound is stably dispersed, the reactivity of the hydrazine compound itself is not impaired, and the activity is increased. A high-contrast image can be obtained. Further, the coating solution of the sample of the present invention is stable even when dissolved over time for a long time,
Extremely excellent production stability.

 ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-56-153336 (JP, A) JP-A-60-140339 (JP, A) JP-A-62-89958 (JP, A) JP-A-63-1988 294552 (JP, A) JP-A-1-235943 (JP, A)

Claims (1)

(57) [Claims] 1. A silver halide photograph comprising a hydrazine compound represented by the following formula (1) and an anionic surfactant represented by the following formula (6) or (7): Photosensitive material. Embedded image In the formula, L ₁ and L ₂ represent —CONR ₇ — groups, —NR ₇ CON
R ₈ — group, —SO ₂ NR ₇ — group or —NR ₇ SO ₂ N
Represents an R ₈ — group, which may be the same or different (here, R ₇ and R ₈ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms) . m is 0 or 1. L ₃ is —CH ₂ CH ₂ O
— Group, —CH ₂ CH (CH ₃ ) O— group, or —CH ₂
It represents _CH (OH) CH 2 O- radical, n is an integer of 3 or more. R ₃ , R ₄ , and R ₅ are a divalent aliphatic group or an aromatic group or a divalent aliphatic group or an aromatic group, or an —O— group, —CO— group, —S— group, or —
It is a divalent group formed by combining an SO— group, a —SO ₂ — group, and a —NR ₉ — group (R ₉ has the same meaning as R ₇ ). R ₆ represents an aliphatic group or an aromatic group. G ₁ represents a —CO— group, a —COCO— group, a —CS— group, a —C (＝ N
G ₂ R ₂ ) — group, —SO— group, —SO ₂ — group or —P
_{(O) (G 2 R 2} ) - represents a group. G ₂ is a single bond,
—O—, —S—, or —N (R ₂ ) —
₂ represents an aliphatic group, an aromatic group or a hydrogen atom, and when a plurality of R ₂ are present in the molecule, they may be the same or different. One of A ₁ and A ₂ is a hydrogen atom, and the other is a hydrogen atom or an acyl group, an alkyl or an arylsulfonyl group. Embedded image Here, R ¹⁰ is a saturated or unsaturated hydrocarbon group having 3 to 20 carbon atoms or a fluorine-substituted product thereof, and R ¹¹ is a hydrogen atom, a methyl group, an ethyl group or a propyl group. M is 1
Is a multivalent alkali metal. n is an integer of 1 to 20. Embedded image R ¹⁰ , M and n have the same meanings as in the general formula (6).
a represents 0.1 or 2, and m is an integer of 1 to 6. "